CN110358339A - Coating fluid and its functional membrane containing liquid crystal capsule - Google Patents
Coating fluid and its functional membrane containing liquid crystal capsule Download PDFInfo
- Publication number
- CN110358339A CN110358339A CN201910265497.2A CN201910265497A CN110358339A CN 110358339 A CN110358339 A CN 110358339A CN 201910265497 A CN201910265497 A CN 201910265497A CN 110358339 A CN110358339 A CN 110358339A
- Authority
- CN
- China
- Prior art keywords
- coating fluid
- liquid crystal
- weight
- formula
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/22—Luminous paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Liquid Crystal (AREA)
- Liquid Crystal Substances (AREA)
Abstract
When liquid crystal capsule is used as display element, adhesive is needed.Especially seek the influence of a kind of pair of electro-optic properties small and adhesive with big voltage retention and high water resistance.There is provided a kind of coating fluid and by being coated with the coating fluid and being subject to drying, irradiation UV etc. and the functional membrane that makes, the coating fluid includes to coat liquid crystal capsule made of liquid-crystal composition and the aqueous solution containing at least one acrylamide monomer as resin.
Description
Technical field
Added the present invention relates to a kind of coating fluid containing polymerizable compound and liquid crystal capsule and by the coating fluid
Work and the functional membrane formed.Electrooptics effect is shown by applying voltage more particularly to a kind of, and then there is big electricity
It presses the functional membrane of conservation rate and the coating fluid containing liquid crystal capsule of the functional membrane can be formed.Coating fluid of the invention exists
The use for forming functional membrane on the way, is expressed as coating liquid sometimes.Adhesive of the invention is the object that liquid crystal capsule is bonded to each other
Matter, and include polymerizable component (also referred to as resin).
Background technique
Liquid crystal capsule with the structure for being surrounded by liquid-crystal composition interior in the hollow space of capsule is used as liquid crystal display member
Part is especially expected to be used for flexible display (such as patent document 1, patent document 2, patent document 3, non-patent literature 1).
A kind of the mixture comprising liquid crystal capsule and adhesive is coated on using rod coater etc. it is known that having
On combed (transverse electric field) substrate, and the liquid crystal display element that only substrate is driven in side.Such liquid crystal display element is benefit
It is driven with Kerr effect (Kerr effect).
When liquid crystal capsule is used for the liquid crystal display element that substrate drives in side such only, if the liquid crystal glue
The average particle diameter of capsule is more than the lower limit (about 380nm) of the wave-length coverage of visible light, then, it is seen that the scattering of light becomes larger, and is difficult to show
Show black.
[existing technical literature]
[patent document]
[patent document 1] Japanese Patent Laid-Open 8-67878
[patent document 2] Japanese Patent Laid-Open 2010-211182
[patent document 3] Ebrean Registered Patent 1506328
[non-patent literature]
[non-patent literature 1] " optics news flash (Optics EXPRESS) " Vol.21, No.13P15719-15727 (1July
2013)
Summary of the invention
[problem to be solved by the invention]
When liquid crystal capsule is used as display element, adhesive is needed.Especially seek the influence of a kind of pair of electro-optic properties
Adhesive small and with big voltage retention and high water resistance.
[technical means to solve problem]
The functional membrane that the inventors of the present invention's human hair is illustrated following coating fluid and is formed using the coating fluid, the painting
Cloth liquid includes by the resin cladding liquid-crystal composition (group including the liquid crystal material comprising one or more kinds of liquid-crystal compounds
Close object) made of liquid crystal capsule and the aqueous solution containing at least one polymerizable compound.
Invention of the present invention including, for example, following form.
Firstly, a kind of coating fluid, be will be coated as resin liquid crystal capsule made of liquid-crystal composition with containing a kind of or
The aqueous solution of two or more polymerizable compounds mixes.It is shape in the following way secondly, a kind of functional membrane
At: the coating fluid is coated on substrate in film-form using rod coater or slit coater etc., after making moisture evaporation, is led to
Cross ultraviolet light (Ultra Violet, UV) etc. irradiation and heating and polymerize.
[The effect of invention]
According to the present invention, the influence that can get to optical characteristics is small and with big voltage retention and high water resistance
Functional membrane and the coating fluid to form the functional membrane.
Detailed description of the invention
Fig. 1 is the structure that alive comb electrode is applied to functional membrane of the invention.
Fig. 2 is the measurement optical system of the optical characteristics evaluation of functional membrane of the invention.
Symbol description
1,2: electrode
3: light source
4: polarizer (polarizer) (Polarizer)
5: glass unit
6: analyzer (polarizer) (Analyzer)
7: optical receiver (Photodetector)
Specific embodiment
The application method of term in this specification is as described below.Sometimes by " liquid-crystal composition " and " liquid crystal display element "
Term be briefly referred to as " composition " and " element "." liquid crystal display element " is liquid crystal display panel and LCD MODULE
General name." liquid crystal compounds " are the compounds with liquid crystalline phases such as nematic phase, smectic phases, though and do not have liquid crystalline phase out
In the characteristic for adjusting nematic temperature range, viscosity, dielectric anisotropy etc purpose and be mixed in the change in composition
Close the general name of object.The compound has the hexatomic ring of such as 1 or 4 cyclohexylidene or Isosorbide-5-Nitrae-phenylene etc, molecular structure
For rodlike (rod like)." liquid crystal capsule " is to coat material made of liquid-crystal composition as resin." polymerizable compound " is
The compound used for the purpose for generating polymer." polymerizable compound " is usually to be used in combination with Photoepolymerizationinitiater initiater, is led to
It crosses and irradiates UV etc. to it and carry out optical free radical polymerization, but optical free radical polymerization may not be defined in.Sometimes formula (1) institute table will be selected from
At least one of group of compound shown compound is referred to as " compound (1) "." compound (1) " refers to formula (1) institute table
A kind of compound shown or two or more compounds.The compound represented by other formulas is also identical.With " being substituted " phase
Close " at least one " refer to not only position, and its number can also be selected unlimitedly.The numerical value for using "~" and indicating
Range refers to comprising numerical value documented by front and back as lower limit value and the range of upper limit value.
Liquid-crystal composition is prepared by mixing plurality of liquid crystals compound.The ratio (content) of liquid crystal compounds
It is by being indicated based on the weight percent (weight %) of the weight of the liquid-crystal composition.Regarding in the liquid-crystal composition needs
Add optically active compound, antioxidant, ultraviolet absorbing agent, pigment, defoaming agent, polymerizable compound, polymerization initiation
The additive of agent, polymerization inhibitor etc.In the same manner as the ratio of liquid crystal compounds, the ratio (additive amount) of additive be by
It is indicated based on the weight percent (weight %) of the weight of liquid-crystal composition.Sometimes also parts per million by weight (ppm) is used.It is poly-
The ratio for closing initiator and polymerization inhibitor is exceptionally to be indicated based on the weight of polymerizable compound.
Sometimes " nematic ceiling temperature " is referred to as " ceiling temperature ".Sometimes referred to as by " nematic lower limit temperature "
For " lower limit temperature "." specific resistance is big " refer to composition in the initial stage not only at room temperature, but also close to nematic
Also there is big specific resistance, and after prolonged use not only at room temperature at a temperature of ceiling temperature, and close to
Also there is big specific resistance at a temperature of the ceiling temperature of column phase." voltage retention is big " be finger element in the initial stage not only
At room temperature, and close to nematic ceiling temperature at a temperature of also have big voltage retention, and for a long time
After use not only at room temperature, and close to nematic ceiling temperature at a temperature of also have big voltage retention.
The statement of " at least one ' A ' can replace through ' B ' " refers to that the quantity of ' A ' is any.It is one in the quantity of ' A '
When, the position of ' A ' be it is any, when the quantity of ' A ' is more than two, their position can also unlimitedly be selected.The rule
Then it is also applied for the statement of " at least one ' A ' replaces through ' B ' ".The statement of " at least one A can replace through B, C or D " refers to packet
Include the case where arbitrary A replaces through B, the case where the case where arbitrary A replaces through C and arbitrary A replace through D and multiple A warp
B, the case where at least two of C, D replace.For example, at least one-CH2In the alkyl that can replace through-O- or-CH=CH-, packet
Include alkyl, alkenyl, alkoxy, alkoxyalkyl, alkoxyalkenyl, alkenyloxy group alkyl.Furthermore continuous two-CH2Warp-O-
The case where replacing and becoming such as-O-O-, be not good enough.
In formula (1), when n is 2, there are two R1.In the compound, two R1It can be identical or also different.
Alkyl is straight-chain or branch-like, and is free of cyclic alkyl.Straight-chain alkyl is typically superior to branch-like alkyl.These
Situation is also identical for the terminal groups of alkoxy, alkenyl etc..
The present invention is following items etc..
1. a kind of coating fluids comprising liquid crystal capsule made of liquid-crystal composition is coated as resin and includes at least one
The adhesive of kind polymerizable compound.
2. coating fluids according to item 1 of item, wherein polymerizable compound is acrylamide compound or methacryl
Amine compounds.
3. coating fluids according to item 1 or item 2 of item, wherein adhesive contains represented as the formula (1) of first composition
At least one compound and formula (2) as second composition represented by least one compound.
(in formula (1) and formula (2), R1And R3It is separately hydrogen or methyl；R2For singly-bound or the alkylene of carbon number 1~20
Base, in the alkylidene, mutually not adjacent arbitrary-CH2It can replace through base represented by-O- or formula (a)；R4For singly-bound
Or the alkylidene of carbon number 1~20, in the alkylidene, mutually not adjacent arbitrary-CH2It can replace through-O-；Z1For-NH-
Or-O-；N is 1,2 or 3,
In formula (a), R5For hydrogen or methyl)
4. coating fluids according to item 3 of item, wherein adhesive contains the R in the formula (1) as first composition1It is all
At least one compound of hydrogen and as the R in the formula (2) of second composition3For at least one compound of hydrogen.
5. coating fluids according to item 3 or item 4 of item, wherein binding agent based weight, the ratio of first composition is 10
The range of the weight of weight %~80 %, the ratio of second composition are the range of 20 weight of weight %~80 %.
6. coating fluids according to any one of item 3 to item 5 of item, wherein adhesive contains selected from formula (1-1) to formula (1-
4) at least one of group of compound represented by compound is as first composition.
7. coating fluids according to any one of item 3 to item 6 of item, wherein adhesive contains selected from formula (2-1) to formula (2-
3) at least one of group of compound represented by compound is as second composition.
8. coating fluids according to any one of item 3 to item 7, wherein adhesive also contain selected from by tool there are two with
On level-one amine or secondary amine polyfunctional amine and multi-functional thiol composed by least one of group compound as
Three ingredients.
9. coating fluids according to any one of item 3 to item 8 of item, wherein adhesive also contains selected from formula (3-1) to formula
At least one of the group of compound represented by (3-3) compound is as third ingredient.
10. coating fluids according to item 8 or item 9 of item, wherein binding agent based weight, ternary ratio are
The range of 0.1 weight % to 10 weight %.
11. coating fluids according to any one of item 1 to item 10 of item, wherein the weight based on coating fluid, solid component
Concentration is 5 weight % or more.
12. coating fluids according to any one of item 1 to item 11 of item, wherein the weight of the solid component based on coating fluid
Amount, the weight rate of the solid component of the solid component and adhesive of liquid crystal capsule are 5:5 to 9:1.
13. coating fluids according to any one of item 1 to item 12 of item, wherein being dispersed with by melamine resin covering liquid
Liquid crystal capsule made of brilliant composition.
14. coating fluids according to any one of item 1 to item 13 of item, wherein the average particle diameter of liquid crystal capsule is 10nm
~380nm.
A kind of 15. functional membranes of item, are formed using the coating fluid according to any one of item 1 to item 14.
16. functional membranes according to item 15 of item, are in the following way and are formed: will be coated with using coating unit
Liquid is made for film-form, after making moisture evaporation by heating, is polymerize by the irradiation of UV etc..
17. functional membranes according to item 15 or item 16 of item, film thickness are 0.5 μm or more.
18. functional membranes according to any one of item 15 to item 17 of item show optics change by applying voltage
Change.
1. adhesive (polymerizable component)
In general, liquid crystal capsule obtained is the state being dispersed in water, but can also be added with the solution of adhesive etc.
State uses.In addition, adhesive can be one or more.As adhesive, (methyl) acrylamide, polyethylene can be used
The water soluble compounds such as alcohol (Polyvinyl Alcohol, PVA) or the melamine series that can be used as capsule wall.In addition, can also make
With lotions such as vinyl chloride, vinyl acetate system, acrylic acid series or the silicone-baseds being dispersed in water.In in liquid crystal capsule
The tolerant state not leaked out can then carry out the displacement of the water-soluble matchmaker in dispersion liquid, can also will be dissolved in the solvent replaced
Compound be used as adhesive.In turn, adhesive can also be made to be reacted in process behind.
Adhesive of the invention contains multifunctional poly- represented by least one polymerizable compound, at least one formula (1)
Simple function polymerizable compound represented by conjunction property compound and at least one formula (2).Optionally, can also in turn containing selected from by
In group composed by polyfunctional amine and multi-functional thiol with more than two level-one amine or secondary amine represented by formula (3)
At least one compound.
Adhesive of the invention is preferred are as follows: in the functional membrane formed using it, in order to make the dispersion of liquid crystal capsule
Property good, good to the adhesion of substrate, after polymerization the water resistance of good, film surface it is good (water-repellancy it is good and
Do not absorb water), electro-optic properties are not impacted, the value and liquid crystal capsule of optical anisotropy and dielectric anisotropy these
Be worth it is similar, and have big voltage retention.
In the adhesive of this invention, in order to ensure functional film strength, first composition is preferably 10 weight %~80
Weight %, and then the preferably 20 weight % of weight %~80, particularly preferably 25 weight of weight %~75 %.
In the adhesive of this invention, in order to make to become good to the adhesion of substrate, second composition be preferably 20 weight %~
80 weight %, and then preferably 25 weight of weight %~75 %.
As first composition, compound represented by following formula (1) can be enumerated.
(in formula (1), R1It independently is hydrogen or methyl；R2For singly-bound or the alkylidene of carbon number 1~20, in the alkylidene
In, mutually not adjacent arbitrary-CH2It can replace through base represented by-O- or formula (a)；N is 1,2 or 3；In formula (a), R5
For hydrogen or methyl)
Wherein, in R2In the case where for alkylidene, the end of the alkylidene replace through base represented by formula (a) and with phase
The case where adjacent NH is composed as-N-N- be not good enough.
As first composition, in compound represented by formula (1), preferably represented by following formula (1-1) to formula (1-4)
Compound.
Preferably at least one of first composition is compound represented by formula (1-1).
As second composition, compound represented by following formula (2) can be enumerated.
(in formula (2), R3For hydrogen or methyl；R4For singly-bound or the alkylidene of carbon number 1~20, in the alkylidene, phase
Arbitrary-the CH not abutted mutually2It can replace through-O-；Z1For-NH- or-O-)
Wherein, in R4In the case where for alkylidene, the end warp-O- of the alkylidene replaces and combines with adjacent-OH
And the case where becoming-O-O-, is not good enough.
As second composition, in compound represented by formula (2), preferably represented by following formula (2-1) to formula (2-3)
Compound.
1-1. crosslinking agent
In order to form firm functional membrane, can be used together with adhesive as ternary crosslinking agent.As friendship
The polyfunctional amine with more than two level-one amine or secondary amine of connection agent and multi-functional thiol can be used alone, can also and with more
Kind.In the case where being used as crosslinking agent, for example, amine or mercaptan are respectively preferably with 2~6.
Total content of polyfunctional amine and multi-functional thiol with more than two level-one amine or secondary amine has no especially
Limitation, in order to make functional film strength and water resistance become good, preferably 0.1 weight % or more, in order to maintain compatibility and electricity
Conservation rate etc. is pressed, preferably 10 weight % are hereinafter, more preferably 0.5 weight of weight %~5 %.
1-1-1. polyfunctional amine
Polyfunctional amine at least two level-one amine or secondary amine is not particularly limited, as long as in the molecule
Compound with more than two level-one amine or secondary amine.In addition, also may include level-one amine and two in polyfunctional amine
Both grade amine.
As the polyfunctional amine with level-one amine, preferably bis- (3- aminopropyl) ethers of hexamethylene diamine, diethylene glycol.
1-1-2. multi-functional thiol
Multi-functional thiol is not particularly limited, as long as in the molecule with the compound of more than two mercaptan.
As multi-functional thiol, preferably 1,6- hexanedithiol.
As third ingredient, compound represented by formula (3-1) to formula (3-3) can be enumerated.
1-2. Photoepolymerizationinitiater initiater
In order to function in binder aqueous solution, Photoepolymerizationinitiater initiater used in the present invention is preferably water-soluble
Property.Specifically, it is preferable that securely (DAROCUR) for gorgeous good solid (IRGACURE) 2959, gorgeous good solid (IRGACURE) MBF, moral
1173, gorgeous good solid (IRGACURE) 754 etc., particularly preferably gorgeous good solid (IRGACURE) 2959.
In order to cause polymerization, it is generally desirable to use the Photoepolymerizationinitiater initiater of appropriate amount.Solid component weight based on coating fluid
Amount, preferably 0.1 parts by weight~10 parts by weight, more preferably 0.5 parts by weight~7 parts by weight.If the range, then remained
Photoepolymerizationinitiater initiater electro-optic properties will not be impacted.
In the present invention, so-called solids by weight indicates the weight from the entirety such as liquid crystal capsule aqueous dispersions or coating fluid
The weight of ingredient obtained by the weight of volatile ingredient is removed, the solids by weight of liquid crystal capsule is from liquid crystal capsule aqueous dispersions
Weight obtained by volatile ingredient (moisture) is removed, the solids by weight of the raw material of adhesive is the aqueous solution of raw material of Autoadhesive
Weight obtained by (aqueous dispersions) (including crosslinking agent, coalescing agent, polymerization initiator, additive) removal volatile ingredient (moisture)
Amount.In addition, the solid component concentration of coating fluid is from liquid crystal capsule moisture when the weight of coating fluid entirety is set as 100%
Aqueous solution of raw material (aqueous dispersions) (including crosslinking agent, coalescing agent, polymerization initiator, additive) removal of dispersion liquid and adhesive
Weight % obtained by volatile ingredient (moisture).
In coating fluid of the invention, for the viewpoint being film-made, solid component concentration is 5 weight % or more, is just coated with
For the viewpoint of the storage stability of liquid, solid component concentration is 60 weight % or less.More preferably 10 weight % or more, 50 weights
% is measured hereinafter, being in turn preferably 15 weight % or more, 40 weight % or less.If the range, then the guarantor of film or coating fluid
It deposits and has good stability.
2. liquid crystal capsule
Liquid crystal capsule of the invention includes the liquid crystal combination containing liquid crystal material as shown in WO2016/035453A1 etc.
Object, surfactant and capsule wall.Specifically, capsule wall is closed surface shape, liquid-crystal composition is configured at the inside of capsule wall.
In addition, being configured with the hydrophobic parts of surfactant in turn in the inside of capsule wall, surface is configured in the outside of capsule wall
The hydrophily base of activating agent.As the concrete example of closed surface shape, spherical surface, ellipsoidal surface etc. can be enumerated.The composition of capsule wall has no
It is particularly limited to, but preferably polymer, and then preferably melamine polymers.
Liquid crystal material is the material comprising one or more kinds of liquid-crystal compounds.In addition, surfactant can be one
Kind compound, also may include multiple compounds.
Relative to the entire amount of liquid crystal capsule, the content of the liquid crystal material in liquid crystal capsule of the invention is preferably 50 weights
Measure the weight % of %~90, more preferably 55 weight of weight %~80 %.If the range of the intensive quantity, then can get sufficient
Liquid crystal property, and the relative thickness of capsule wall becomes abundant and is difficult to be destroyed.
Relative to liquid crystal material, the content of surfactant is preferably the 1 weight % of weight %~50, and then preferably 5 weights
Measure the weight of %~40 %.Relative to liquid crystal material, the content of capsule wall is preferably the 1 weight % of weight %~60, and then preferably 5
The weight of weight %~45 %.
The average particle diameter of liquid crystal capsule is 10nm~380nm.For the viewpoint of display quality, liquid crystal capsule is averaged
Particle diameter is preferably 30nm~250nm, and then preferably 30nm~200nm.Furthermore in this specification, so-called " average particle
Diameter " is the average value that light scattering determining 50 times resulting particle diameters are utilized at 25 DEG C.
Liquid-crystal composition can be used as having nematic composition, and can be used as light by addition optically active compound
Learn active composition.
2-1. liquid-crystal composition
Liquid-crystal composition includes liquid crystal material, can and then arbitrarily include optically active compound, antioxidant, ultraviolet light
The additives such as absorbent, dichroism pigment.
If the compatibility of liquid crystal material contained in liquid-crystal composition and monomer is well and in water slightly solubility, have no
It is particularly limited to.In addition, the liquid-crystal composition comprising liquid crystal material can for example be enumerated: nematic liquid crystal, Smectic liquid crystal, cholesteric liquid
Crystalline substance, Chiral Nematic liquid crystals etc..In these compositions, preferably nematic liquid crystal.
Liquid crystal material includes preferably the different liquid-crystal compounds of characteristic.Specifically, it is preferable that for about on nematic
Limiting temperature, viscosity, optical anisotropy, dielectric anisotropy, specific resistance etc. has defined characteristic.
Furthermore for the viewpoint of specific resistance or voltage retention, it is however preferred to have the ratio of the compound of cyano is opposite
In liquid-crystal composition entirety less than 3 weight %.
(1) positive type liquid crystal material contained in liquid-crystal composition
The positive type liquid crystal composition that dielectric anisotropy is positive mainly has about -10 DEG C of nematic lower limit temperature below
Degree, about 70 DEG C or more of ceiling temperature, about 0.20 to about 0.35 range optical anisotropy and about 8 to about 40 model
The dielectric anisotropy enclosed.Element containing liquid-crystal composition has big voltage retention.The composition is suitable for active
Matrix (Active Matrix, AM) element, the AM element particularly suitable for infiltration type.
Positive type liquid crystal composition preferably only includes positive type liquid crystal compound, and then preferably includes positive type liquid crystal compound
It is zero or almost nil liquid crystal compounds with dielectric anisotropy.
(2) negative type liquid crystal material contained in liquid-crystal composition
The negative type liquid crystal composition that dielectric anisotropy is negative has about -10 DEG C of nematic lower limit temperatures below, about
70 DEG C or more of ceiling temperature, about 0.08 to about 0.35 range optical anisotropy and about -2 to about -20 range
Dielectric anisotropy.Element containing liquid-crystal composition has big voltage retention.The composition is suitable for AM element, special
It is not suitable for the AM element of infiltration type.
Negative type liquid crystal composition preferably only includes negative type liquid crystal compound, and then preferably includes negative type liquid crystal compound
It is zero or almost nil liquid crystal compounds with dielectric anisotropy.
Can WO2015/162950A1, WO2016/ be specifically recorded in for the liquid-crystal composition of liquid crystal capsule particularly suitablely
In 063585A1, Japanese Patent Laid-Open 2017-222778 etc..
2-2. surfactant
If surfactant used in the manufacture of liquid crystal capsule has surface-active, it is not particularly limited, but excellent
It is selected as affine with both surfaces of liquid crystal material and capsule wall.
With the affine surfactant in both surfaces of liquid crystal material and capsule wall be shared hydrophobicity with it is hydrophilic
Compound, such as can enumerate: glycerol, ethylene glycol, diethylene glycol, single ether, butanediol, propylene glycol, propionic acid pentanediol etc., as
Surfactant used in the manufacture of liquid crystal capsule, it is preferable to use electron donating property monomer and Malaysia in free radical polymerization
The hydrolysate of the copolymer of acid anhydrides and similar polymer, more preferably using the styrene and Malaysia that can have substituent group
The hydrolysate and alkenyl of the copolymer of acid anhydrides and similar polymer and the copolymer of maleic anhydride and similar
The hydrolysate of polymer, particularly preferably using the hydrolysate of styrene-maleic anhydride copolymer and similar polymer,
And the hydrolysate of 1- octadecylene-copolymer-maleic anhydride and similar polymer.In addition, it is possible to use 2- ethylhexyl
The hydrolysate of vinyl ether-maleic acid copolymer and similar polymer.
The weight average molecular weight of surfactant of the invention is preferably 1,000~500,000, particularly preferably 5,
000~50,000.It if the range, is then completely dissolved in water, and rises there is no viscosity and be difficult to the case where mixing.
2-3. capsule wall
Monomer used in the manufacture of liquid crystal capsule and prepolymer are the material of the capsule wall of liquid crystal capsule.That is, utilizing
(in-situ) polymerization in situ, is polymerize in such a way that monomer and prepolymer are packed in liquid-crystal composition, and forms closed surface shape
Capsule wall.If monomer and prepolymer have polymerization base, it is not particularly limited.
It as being used as the monomer or prepolymer of capsule wall in the manufacture of liquid crystal capsule, such as can enumerate: gelatin, amide tree
Rouge, silicone resin, phenolic resin, carbamide resin, melamine resin, melamine phenolic resin, gathers carbamate resins
Ester resin, diallyl phthalate resin or epoxy resin etc..Capsule used in manufacture as liquid crystal capsule
Wall, it is preferable to use melamine resin or urea-formaline resin.Capsule wall more preferably is melamine resin.
3. other additives
In the case where being coated on the coating fluid containing water on the substrates such as the glass with electrode, due to relative to substrate
Coating fluid surface tension it is high, therefore there are following situations: substrate it is incompatible with coating fluid and can not utilize rod coater or
The coating units such as slit coater are successfully coated.In order to make the coating to substrate become good, surface conditioner can be used
Or thickener.
3-1. surface conditioner
Surface conditioner is to add to reduce the surface tension of coating fluid making to become good to the coating of substrate, can be made
With surfactant or levelling agent.Additive electro-optic properties or voltage retention etc. not impacted particularly preferably,
Specifically, it is preferable that for BYK-UV3530, BYK-348, BYK-381, BYK-3440, F-477, F-553 and F-556 etc., it is more excellent
It is selected as BYK-UV3530, F-477, F-553 and BYK-348.About the content of additive, relative to the moisture of coating fluid, in order to
Surface tension is reduced, more than preferably 0.1 parts by weight, in order to maintain electro-optic properties or voltage retention etc., preferably 10 weights
Measure part or less.
3-2. thickener
Thickener is added to improve the viscosity of coating fluid (relatively reducing the moisture concentration of coating fluid), can be used
Viscoplasticity regulator.Additive electro-optic properties or voltage retention etc. not impacted particularly preferably, specifically,
Preferably SN- thickener (THICKENER) 601, SN- thickener (THICKENER) 612, SN- thickener (THICKENER)
612NC, SN- thickener (THICKENER) 619, SN- thickener (THICKENER) 621N, SN- thickener (THICKENER)
621TF, SN- thickener (THICKENER) 623N, SN- thickener (THICKENER) 625N, SN- thickener (THICKENER)
660T, SN- thickener (THICKENER) 665T, SN- thickener (THICKENER) 615, SN- thickener (THICKENER)
617, SN- thickener (THICKENER) 618, SN- thickener (THICKENER) 630, SN- thickener (THICKENER) 634,
SN- thickener (THICKENER) 636 and SN- thickener (THICKENER) 640, more preferably SN- thickener (THICKENER)
612.About the content of additive, relative to the moisture of coating fluid, in order to reduce surface tension, it is more than preferably 0.1 parts by weight,
In order to maintain electro-optic properties or voltage retention etc., below preferably 10 parts by weight.
It is a small amount of every time in binder aqueous solution about the preparation of coating fluid, such as into stirring that liquid crystal capsule is added dropwise.For
It is homogeneously dispersed in liquid crystal capsule in adhesive, rate of addition is preferably 0.2ml/ seconds hereinafter, mixing time after being added dropwise
Preferably 20 minutes or more.After stirring, in order to remove the gas dissolved in process, decompression or ultrasonic wave are preferably utilized
Carry out bubble removal step.
The formation of functional membrane is to carry out in the following way: using the coating of rod coater or slit coater etc
Coating fluid is coated on substrate (painting process) in film-form, is added using heating plate or circulating thermostat etc. by device
Heat and so that volatile ingredient (mainly moisture) is evaporated (drying process), (polymerization is polymerize by the irradiation or heating of UV etc.
Process).The temperature and time of drying process preferably uses thermogravimetric/differential thermal analyzer (Thermogravimetry/
Differential Thermal Analyzer, TG/DTA) etc. devices determine.In the case where solvent is water, most cases
It is drying temperature is preferably 50 DEG C~100 DEG C, drying time is preferably 30 minutes~120 minutes.The cohesive strength of polymerization process
And the time is affected because of polymerizable component, crosslinking agent, polymerization initiator, therefore preferably uses equation of light scanning calorimeter instrument
Devices such as (Photo Differential Scanning Calorimeter, PhotoDSC) determine.In the feelings of irradiation UV etc.
Under condition, preferably considers the damage to liquid crystal material and use the filter etc. for ending 350nm wave spectrum below.
It is big by application voltage bring in order to obtain about the weight rate of liquid crystal capsule and adhesive in functional membrane
Optical change, the ratio of liquid crystal capsule is preferably 5 one-tenth or more, more preferably 7 one-tenth.On the other hand, in order to maintain functional membrane
Intensity or flexibility, the ratio of adhesive is preferably 2 one-tenth or more, more preferably 4 one-tenth.
About the film thickness of functional membrane, only in the case where the sides substrates such as combed (transverse electric field) substrate are driven,
Sufficient optical change, preferably 0.5 μm or more are obtained in order to apply voltage, and effect is applied by voltage in order to prevent and is not covered
Region caused by transmitance reduction, preferably 10 μm hereinafter, more preferably 1 μm~6 μm.
[embodiment]
By embodiment, the present invention will be described in more detail.The present invention is not limited by these embodiments.This hair
The bright also mixture comprising being mixed at least two of the composition of embodiment.Synthesized compound utilizes nuclear magnetic resonance
The methods of (Nuclear Magnetic Resonance, NMR) analysis is identified.The characteristic of compound, composition and machining object
It is measured using the method for following records.
NMR analysis: the DRX-500 manufactured when measurement using this guest (Bruker BioSpin) company of Brooker Baier.?1In the measurement of H-NMR, sample is made to be dissolved in CDCl3Etc. in deuterates solvent, at room temperature, with 500MHz, cumulative number 16 times
Condition is measured.Use tetramethylsilane as internal standard.?19In the measurement of F-NMR, CFCl is used3As inside
Standard is carried out with cumulative number 24 times.In the explanation of NMR spectrum, s indicates unimodal (singlet), and d indicates bimodal
(doublet), t indicates triplet (triplet), and q indicates quartet (quartet), and quin indicates quintet (quintet),
Sex indicates sextet (sextet), and m indicates multiplet (multiplet), and br indicates broad peak (broad).
Gas chromatographic analysis: the GC-14B type gas chromatograph manufactured when measurement using Shimadzu Seisakusho Ltd..Carrier gas is helium
(2mL/ minutes).Sample evaporation chamber is set as 280 DEG C, will test device (flame ionic detector (Flame Ionization
Detector, FID)) it is set as 300 DEG C.In the separation of component cpd, Anjelen Sci. & Tech. Inc (Agilent is used
Technologies Inc.) manufacture capillary column DB-1 (length 30m, internal diameter 0.32mm, 0.25 μm of film thickness；Fixed liquid phase is
Dimethyl polysiloxane；It is nonpolarity).After the tubing string is kept for 2 minutes at 200 DEG C, it is warming up to 5 DEG C/min of speed
Until 280 DEG C.After sample is prepared into acetone soln (0.1 weight %), its 1 μ L is injected into sample evaporation chamber.Recording gauge
For the C-R5A type chromatograph element (Chromatopac) or its same product of Shimadzu Seisakusho Ltd.'s manufacture.Gas chromatogram obtained
The retention time of peak value corresponding to component cpd and the area of peak value are shown.
Chloroform, hexane etc. can be used in the solvent for diluting sample.For separated component compound, also can be used below
Capillary column.HP-1 (length 30m, the internal diameter of Anjelen Sci. & Tech. Inc (Agilent Technologies Inc.) manufacture
0.32mm, 0.25 μm of film thickness), Rtx-1 (length 30m, the internal diameter of Rui Si Imtech (Restek Corporation) manufacture
0.32mm, 0.25 μm of film thickness), SGE international corporation (SGE International Pty.Ltd) manufacture BP-1 (length 30m,
Internal diameter 0.32mm, 0.25 μm of film thickness).Compound peak value is overlapped in order to prevent, and the capillary of Shimadzu Seisakusho Ltd.'s manufacture also can be used
Tubing string CBP1-M50-025 (length 50m, internal diameter 0.25mm, 0.25 μm of film thickness).
The ratio of liquid crystal compounds contained in composition can be calculated using following method.Utilize gas chromatograph
(FID) mixtures of liquid crystal compounds is detected.The area ratio of peak value in gas chromatogram is equivalent to liquid crystal compounds
Ratio (weight ratio).When using the above documented capillary column, the correction coefficient of various liquid crystal compounds can be regarded
It is 1.Therefore, the ratio (weight %) of liquid crystal compounds can be calculated according to the area ratio of peak value.
It measures sample: when measuring the characteristic of composition, composition being directly used as sample.When the characteristic of measurement compound
When, measurement sample is prepared by mixing the compound (15 weight %) into mother liquor brilliant (85 weight %).According to logical
It crosses and measures value obtained, the characteristic value of compound is calculated using extrapolation.(extrapolated value)={ (measured value of sample)-
0.85 × (measured value of mother liquor crystalline substance) }/0.15.Under the ratio, when smectic phase (or crystallization) is precipitated at 25 DEG C, it will change
The ratio for closing object and mother liquor crystalline substance is successively changed to 10 weight %:90 weight %, 5 weight %:95 weight %, 1 weight %:99 weight
Measure %.Found out using the extrapolation ceiling temperature relevant to compound, optical anisotropy, viscosity and dielectric respectively to
Anisotropic value.
It is brilliant using following mother liquors.The ratio of component cpd is indicated by weight %.
Measuring method: the measurement of characteristic is carried out using following methods.These methods are mostly by civic organization's e-mail
Cease technical industry association (Japan Electronics and Information Technology Industries
Association；Hereinafter referred to as JEITA) review documented side in the JEITA specification (JEITAED-2521B) formulated
Method or the method that it is modified.Thin film transistor (TFT) (Thin Film is not installed in the TN element for measurement
Transistor, TFT).
(1) nematic ceiling temperature (NI；DEG C): sample is placed in adding for the melting point apparatus for having petrographic microscope
On hot plate, heated with 1 DEG C/min of speed.Measure sample a part from nematic phase change be isotropic liquid when
Temperature.
(2) nematic lower limit temperature (TC；DEG C): there will be nematic sample to be put into vial, in 0 DEG C, -10
DEG C, -20 DEG C, take care of 10 in the freezer units of -30 DEG C and -40 DEG C after, observe liquid crystalline phase.For example, when sample is protected at -20 DEG C
It holds nematic phase and variation is for crystallization or when smectic phase at -30 DEG C, by TCIt is recorded as < -20 DEG C.
(3) viscosity (block viscosity；η；It is measured at 20 DEG C；MPas): Tokyo gauge share limited public affairs are used when measurement
Take charge of the E type rotational viscometer of manufacture.
(4) viscosity (rotary viscosity；γ1；It is measured at 20 DEG C；MPas): according to " dividing for M. the present well (M.Imai) et al.
Sub- crystal and liquid crystal (Molecular Crystals and Liquid Crystals) ", Vol.259,37 (1995) is middle to be remembered
The method of load is measured.It is 0 ° and the interval (cell gap) of 2 sheet glass substrates is 5 μm that sample, which is put into twist angle,
In TN element.In the range of 16V~19.5V, voltage is applied to the element stage as unit of 0.5V.Do not applying
After voltage 0.2 second, only to apply 1 rectangular wave (rectangular pulse；0.2 second) with the condition for not applying (2 seconds) apply voltage repeatedly.
Measurement by the peak point current (peak current) of transient current caused by the application (transient current) and
Time to peak (peak time).According to calculating formula documented by page 40 in the paper of these measured values and M. the present well et al.
(8) value of rotary viscosity is obtained.The value of dielectric anisotropy needed for the calculating is viscous using the rotation is determined
The element of degree is found out using following documented method.
(5) optical anisotropy (refractive anisotrop；Δn；Measured at 25 DEG C): using the light of wavelength 589nm, lead to
It crosses and the Abbe refractometer of polarizer is installed on ocular lens to be measured.In one direction behind the surface of friction headprism,
Sample is added dropwise on headprism.Refractive index n ∥ is measured when the direction of polarisation is parallel with the direction of friction.When the direction of polarisation
Refractive index n ⊥ is measured when vertical with the direction of friction.Optically anisotropic value is counted according to the formula of Δ n=n ∥-n ⊥
It calculates.In the mode using the optical change as caused by Kerr effect, it is generally desirable to which optical anisotropy is with dielectric respectively to different
The product of property is big, therefore preferably optical anisotropy is as big as possible.Optical anisotropy is preferably 0.20~0.35 range,
Preferably 0.23~0.32 range in turn.
(6) dielectric anisotropy (Δ ε；Measured at 25 DEG C): sample is put into the interval (unit of 2 sheet glass substrates
Gap) it is in TN element that 9 μm and twist angle are 80 degree.Sine wave (10V, 1kHz) is applied to the element, is measured after 2 seconds
Dielectric constant (ε ∥) on the long axis direction of liquid crystal molecule.Sine wave (0.5V, 1kHz) is applied to the element, is measured after 2 seconds
Dielectric constant (ε ⊥) on the short-axis direction of liquid crystal molecule.The value of dielectric anisotropy is the formula according to Δ ε=ε ∥-ε ⊥
To calculate.In order to reduce driving voltage, it is generally desirable to which dielectric anisotropy is big.Especially passing through polymer-stabilized or capsule
In the mode to limit the electric field applied to liquid-crystal composition such as change, there are the tendencies that driving voltage is got higher, therefore are preferably situated between
Electrical anisotropy is as big as possible.In addition, in the mode using the optical change as caused by Kerr effect, it is generally desirable to optics
The product of anisotropy and dielectric anisotropy is big, therefore preferably dielectric anisotropy is as big as possible.Dielectric anisotropy is excellent
It is selected as 8~40 range, and then preferably 10~30 range.
(7) threshold voltage (Vth；It is measured at 25 DEG C；V): being manufactured when measurement using great Zhong electronics limited liability company
LCD5100 type luminance meter.Light source is halogen lamp.It is 0.45/ Δ that sample, which is put into the interval (cell gap) of 2 sheet glass substrates,
In the TN element of n (μm), twist angle for 80 degree of normal white mode (normally white mode).It is applied to the element
Voltage (32Hz, rectangular wave) is as unit of 0.02V, until periodically increasing to 10V from 0V.At this point, from vertical direction pair
Element irradiation light, and measure the light quantity through element.It is 100%, the light quantity that transmitance when the light quantity reaches maximum, which is made,
Voltage-transmittance curve that transmitance is 0% when minimum.Threshold voltage is voltage when reaching 90% by transmitance to indicate.
(8) elastic constant (K；It is measured at 25 DEG C；PN): Yokogawa Hewlett-Packard (Yokogawa Hewlett is used when measurement
Packard) the HP4284A type LCR meter of limited liability company's manufacture.Sample is put into the interval to 2 sheet glass substrates (between unit
Gap) in 20 μm of horizontal alignment element.0 volt~20 volts of charge is applied to the element, and measure electrostatic capacitance and
Apply voltage.Utilize " liquid crystal device handbook (Liquid Crystal Device Handbook) " (Nikkan Kogyo Shimbun) the
Formula (2.98), formula (2.101) in page 75 are fitted the electrostatic capacitance (C) measured with the value for applying voltage (V), and root
The value of K11 and K33 is obtained according to formula (2.99).Then, the value of calculated in the past K11 and K33 are used for " liquid crystal device handbook "
K22 is calculated in formula (3.18) in page 171.Elastic constant is by the flat of K11, K22 and K33 for finding out in this way
Mean value indicates.
(9) specific resistance (ρ；It is measured at 25 DEG C；Ω cm): sample 1.0mL is injected into the container for having electrode.To institute
It states container and applies DC voltage (10V), and the DC current after measurement 10 seconds.Specific resistance calculates according to the following formula.(specific resistance)
={ (voltage) × (capacitor of container) }/{ (DC current) × (dielectric constant of vacuum) }.
(10) scanning electron microscope (Scanning Electron Microscope, SEM) is observed: using die coating cloth
Liquid crystal capsule aqueous dispersions coated on high-quality neutralized paper or glass, are used heating plate by machine, spin coater or rod coater
Or drying machine makes the moisture in liquid crystal capsule aqueous dispersions evaporate and make sample.Sample SEM is fixed on using conductive strips to see
It examines on sample table, uses sputtering equipment (Hitachi's new and high technology (Hitachi High-Technologies) limited liability company
Manufacture: E-1045) vapor deposition platinum.The sample table is installed on SEM (Hitachi's new and high technology (Hitachi High-
Technologies) limited liability company manufactures: on SU-70).Acceleration voltage (0.5kV~1.0kV), multiplying power (1k are changed on one side
~50k) etc., sample is observed on one side.
(11) it the average particle diameter measurement of capsule: in the present invention, is manufactured using Ji Zhuan limited liability company when measurement
Dynamic light scattering formula grain size analysis meter (nano Tyke (nanotrac) UPA).Ultrapure water is prepared by by liquid crystal capsule moisture
Dispersion liquid is diluted to the sample of concentration appropriate, measures average particle diameter at 25 DEG C.
(12-1)T0And T100Setting
As shown in Fig. 2, optical system is by being attached to petrographic microscope (the cruel Li Kesi of Chinese mugwort of Nikon (Nikon) manufacture
(ECLIPSE) LV100POL) light emitting diode (Light Emitting Diode, LED) light source (3) (KLV manufacture
B180-5600K), polarizer (Polarizer) (4), analyzer (Analyzer) (6), the glass unit (5) with comb electrode
And photo-detector (7) is constituted, glass unit (5) is the line direction with comb electrode (electrode 1,2) shown in FIG. 1 relative to respective
Polarizer and as 45 ° mode and with the incident angle of light source (3) become vertical mode be arranged.It is using flash ranging through light
Device (7) (3298F of Yokogawa (YOKOGAWA) manufacture) is determined to measure, and penetrates light settings for what is measured with cross Nicols as transmission
0% (T of rate0), light settings are penetrated as 100% (T of transmitance by what is measured using parallel Nicolle100)。
(12-2)V10、Tmin、TmaxMeasurement
Using Arbitrary Waveform Generator (33220A of peace Jie Laimute (Agilemt) manufacture) and bipolar power supply, (NF is manufactured
HSA4051) to be formed with functional membrane have comb electrode glass unit apply voltage (rectangular wave (60Hz)), will transmit through
The voltage that rate rises to 10% is set as V10(unit: V).In addition, transmitance when applying 0V voltage is set as Tmin(unit: %),
Maximum transmitance will be become and be set as Tmax(unit: %).
(13) film thickness measuring (unit: μm)
There is the functional property film of self-forming a part of the glass unit of comb electrode to eliminate functional membrane, and utilize fine
Shape measuring apparatus Alpha's step instrument (Alpha Step) IQ of manufacture (Ke Lei (KLATENCOR) (stock)) measures its scale
And determine film thickness.
(14) measurement (unit: %) of solid component concentration
The solid component concentration of coating fluid comprising liquid crystal capsule and adhesive is that (Shimadzu Seisakusho Ltd. manufactures using moisture meter
MOC63u) measure.
1. the preparation of liquid crystal capsule A
By styrene-maleic anhydride copolymer (the molecular weight about 350,000) aqueous solution (160g) and ultrapure water of 5.24wt%
(70g) is put into stainless steel beaker, is stirred using homogenizer (IKAT25).Put into liquid below on a small quantity every time thereto
After brilliant composition 1 (40g), stirs 3 minutes and emulsified.By the emulsion (226.6g) investment to the weary spy of nano
(NanoVater) in (the mechanical industrial limited liability company of Jitian: NVL-ES008-D), and pass through 3 at extrusion pressure 150MPa
It is secondary.(process C) thereafter, is heated to 80 DEG C, and using blender, (new east (HEIDON) is manufactured: high power Universal stirring machine on one side
BLh1200 it) is stirred, puts into melamine pre-polymer (8.4g) on one side, stir 2 hours.Restore reaction mixture to room
Wen Hou is adjusted to pH value 7 using 10wt% sodium hydrate aqueous solution, obtains liquid crystal capsule aqueous dispersions.
It is prepared by the sample that liquid crystal capsule aqueous dispersions are diluted to concentration appropriate by ultrapure water, fills share using day machine
The dynamic light scattering formula grain size analysis meter (nano Tyke (nanotrac) UPA) of Co., Ltd's manufacture is observed, and is as a result confirmed
To the liquid crystal capsule of average particle diameter about 200nm.
2. the preparation of liquid crystal capsule B
By styrene-maleic anhydride copolymer (the molecular weight about 5,500) aqueous solution (44.0g) and ultrapure water of 13.6wt%
(76.0g) is put into stainless steel beaker, is stirred using homogenizer (IKAT25).It is a small amount of every time thereto to put into liquid crystal group
After closing object 1 (18g), stirs 3 minutes and emulsified.By the emulsion (126.5g) investment to star burst (Starburst) (China fir
Wild machinery (Sugino Machine) limited liability company: HJP-25001) in, and pass through 3 times at extrusion pressure 150MPa.
Thereafter, 70 DEG C are heated to, (new east (HEIDON) manufactures: high power Universal stirring machine BLh1200) carrying out using blender on one side
Stirring puts into melamine pre-polymer (6.6g) on one side, after stirring 15 minutes, is warming up to 80 DEG C and stirs 105 minutes.Make to react
Mixture restores to room temperature, is adjusted to pH value 7 using 1.00wt% aqueous ammonium, obtains liquid crystal capsule aqueous dispersions.
It is prepared by the sample that liquid crystal capsule aqueous dispersions are diluted to concentration appropriate by ultrapure water, fills share using day machine
The dynamic light scattering formula grain size analysis meter (nano Tyke (nanotrac) UPA) of Co., Ltd's manufacture is observed, and is as a result confirmed
To the liquid crystal capsule of average particle diameter about 130nm.
3. the preparation of liquid crystal capsule C
By 1- octadecylene-copolymer-maleic anhydride (molecular weight about 36,000) aqueous solution (148.0g) of 6.1wt% and surpass
Pure water (2.0g) is put into stainless steel beaker, is stirred using homogenizer (IKAT25).It is a small amount of every time thereto to put into liquid
After brilliant composition 1 (27.8g), stirs 3 minutes and emulsified.By the emulsion (166.8g) investment to star burst
(Starburst) in (wild mechanical (Sugino Machine) limited liability company of China fir: HJP-25001), and in extrusion pressure
Pass through 5 times under 150MPa.Thereafter, 70 DEG C are heated to, (new east (HEIDON) manufactures: high power is general to be stirred using blender on one side
Mix machine BLh1200) it is stirred, melamine pre-polymer (11.1g) is put on one side, after stirring 15 minutes, is warming up to 80 DEG C simultaneously
Stirring 105 minutes obtains liquid crystal capsule aqueous dispersions.
It is prepared by the sample that liquid crystal capsule aqueous dispersions are diluted to concentration appropriate by ultrapure water, fills share using day machine
The dynamic light scattering formula grain size analysis meter (nano Tyke (nanotrac) UPA) of Co., Ltd's manufacture is observed, and is as a result confirmed
To the liquid crystal capsule of average particle diameter about 170nm.
[liquid-crystal composition 1]
NI=90.0 DEG C；Tc<-20℃；Δ n=0.246；Δ ε=9.4；Vth=1.88V；η=42.7mPas.
Description Method of the mark of the compound according to following Table As.
4. the preparation of coating fluid
The composition of prepared coating fluid is shown in Table 1.Numerical value in table is the weight % of the solid component of each ingredient.
Binder aqueous solution (or aqueous dispersions) of the preparation comprising compound represented by formula (1-1) etc., utilizes magnetic stirrer etc. on one side
It is stirred and is mixed on one side, so as to be homogeneously dispersed in by the liquid crystal capsule aqueous dispersions of resin cladding liquid-crystal composition 1
In binder aqueous solution.The mixed liquor is depressurized for by the purpose of the gas removal in bubble or water (for example, decompression
Degree: 1kPa, decompression time: 30 minutes).Relative to adhesive weight and the Photoepolymerizationinitiater initiater that adds 7 parts by weight is gorgeous good solid
(Irgacure)2959。
The composition of [table 1] coating fluid
5. the formation of functional membrane
It is selected using automatic coating machine (RK company manufactures: K controls coating machine) and in a manner of becoming defined film thickness
Coating fluid shown in table 1 is carried out film on the glass unit with comb electrode by bar.Using heating plate, (set temperature is
50 DEG C) heating 30 minutes and by moisture removal.In a nitrogen environment, using 350nm or less cut-off filter to the glass list
Member carries out UV exposure (the accumulative light quantity 1200mJ under 365nm), polymerization reaction is thus carried out, to form functional membrane.
6. the evaluation of physical property of functional membrane
By functional membrane formed in 1~embodiment of embodiment 11 evaluation result is shown in table in 2.
The evaluation result of [table 2] functional membrane
7. the preparation of coating fluid
The composition of prepared coating fluid is shown in Table 3.Numerical value in table is the weight % of the solid component of each ingredient.
Binder aqueous solution (or aqueous dispersions) of the preparation comprising compound represented by formula (1-1) etc., utilizes magnetic stirrer etc. on one side
It is stirred and is mixed on one side, so as to be homogeneously dispersed in by the liquid crystal capsule aqueous dispersions of resin cladding liquid-crystal composition viscous
In mixture aqueous solution.The mixed liquor for by bubble or water gas removal purpose and be depressurized (for example, degree of decompression:
1kPa, decompression time: 30 minutes).In addition, relative to adhesive weight and the Photoepolymerizationinitiater initiater that adds 3.5 parts by weight is gorgeous
Good solid (Irgacure) 2959, and the surface conditioner BYK-UV3530 of 0.5 parts by weight is added relative to moisture.
The composition of [table 3] coating fluid
8. the formation of functional membrane
It is selected using automatic coating machine (RK company manufactures: K controls coating machine) and in a manner of becoming defined film thickness
Coating fluid shown in table 3 is carried out film on the glass unit with comb electrode by bar.Using heating plate, (set temperature is
60 DEG C) heating 30 minutes and by moisture removal.In a nitrogen environment, using 350nm or less cut-off filter to the glass list
Member carries out UV exposure (the accumulative light quantity 1200mJ under 365nm), polymerization reaction is thus carried out, to form functional membrane.Implement
In example 18, is further heated 3 hours in heating plate (set temperature: 100 DEG C), polymerization reaction is thus carried out, to form function
It can property film.
9. the evaluation of physical property of functional membrane
By functional membrane formed in 12~embodiment of embodiment 18 evaluation result is shown in table in 4.
The evaluation result of [table 4] functional membrane
Adhesive according to the present invention can prepare the functional membrane for being uniformly dispersed liquid crystal capsule, and to the function
Property film apply voltage when, obtain good optical characteristics.
[industrial availability]
The functional membrane shows optical isotropy, can be in the liquid crystal by showing optically isotropic liquid crystal layer driving
It is utilized in display element.In turn, can switch in in-plane switching (in-plane switching, IPS) mode or fringing field
It is used in the element of (Fringe Field Switching, FFS) mode.The element has good optical characteristics.
Claims (18)
1. a kind of coating fluid, which is characterized in that including coating liquid crystal capsule made of liquid-crystal composition as resin and comprising extremely
A kind of adhesive of few polymerizable compound.
2. coating fluid according to claim 1, which is characterized in that the polymerizable compound be acrylamide compound or
Methacrylamide compounds.
3. coating fluid according to claim 1 or 2, which is characterized in that described adhesive contains the formula as first composition
(1) at least one compound represented by least one compound represented by and the formula (2) as second composition；
In formula (1) and formula (2), R1And R3It is separately hydrogen or methyl；R2For singly-bound or the alkylidene of carbon number 1~20,
In the alkylidene, mutually not adjacent arbitrary-CH2It can replace through base represented by-O- or formula (a)；R4For singly-bound or carbon
The alkylidene of number 1~20, in the alkylidene, mutually not adjacent arbitrary-CH2It can replace through-O-；Z1For-NH- or-
O-；N is 1,2 or 3,
In formula (a), R5For hydrogen or methyl.
4. coating fluid according to claim 3, which is characterized in that described adhesive contains the formula as the first composition
(1) R in1At least one compound of all hydrogen and as the R in the formula (2) of the second composition3For at least one of hydrogen
Compound.
5. coating fluid according to claim 3, which is characterized in that the weight based on described adhesive, the first composition
Ratio be 10 weight of weight %~80 % range, the ratio of the second composition is the model of 20 weight of weight %~80 %
It encloses.
6. coating fluid according to claim 3, which is characterized in that described adhesive contains selected from formula (1-1) to formula (1-4)
At least one of represented group of compound compound is as the first composition；
7. coating fluid according to claim 3, which is characterized in that described adhesive contains selected from formula (2-1) to formula (2-3)
At least one of represented group of compound compound is as the second composition；
8. coating fluid according to claim 3, which is characterized in that described adhesive also contains selected from by having two or more
Level-one amine or secondary amine polyfunctional amine and multi-functional thiol composed by least one of group compound as third
Ingredient.
9. coating fluid according to claim 3, which is characterized in that described adhesive also contains selected from formula (3-1) to formula (3-
3) at least one of group of compound represented by compound is as third ingredient；
10. coating fluid according to claim 8 or claim 9, which is characterized in that the weight based on described adhesive, the third
The ratio of ingredient is the range of 0.1 weight % to 10 weight %.
11. coating fluid according to claim 1 or 2, which is characterized in that the weight based on the coating fluid, solid component
Concentration is 5 weight % or more.
12. coating fluid according to claim 1 or 2, which is characterized in that the weight of the solid component based on the coating fluid
Amount, the weight rate of the solid component of the solid component and described adhesive of the liquid crystal capsule are 5:5 to 9:1.
13. coating fluid according to claim 1 or 2, which is characterized in that be dispersed with and coat liquid crystal group by melamine resin
Close liquid crystal capsule made of object.
14. coating fluid according to claim 1 or 2, which is characterized in that the average particle diameter of the liquid crystal capsule is 10nm
~380nm.
15. a kind of functional membrane, which is characterized in that it is using according to claim 1 to coating fluid described in any one of 14
And it is formed.
16. functional membrane according to claim 15, which is characterized in that it is to be formed in the following way: using painting
Coating fluid is made for film-form by coating device, after making moisture evaporation by heating, is polymerize by the irradiation of ultraviolet light etc..
17. functional membrane according to claim 15 or 16, which is characterized in that film thickness is 0.5 μm or more.
18. functional membrane according to claim 15 or 16, which is characterized in that show optics change by applying voltage
Change.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018074690 | 2018-04-09 | ||
| JP2018-074690 | 2018-04-09 | ||
| JP2019-032357 | 2019-02-26 | ||
| JP2019032357A JP2019185024A (en) | 2018-04-09 | 2019-02-26 | Coating liquid containing liquid crystal capsules, and functional film produced therewith |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110358339A true CN110358339A (en) | 2019-10-22 |
Family
ID=68215537
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910265497.2A Pending CN110358339A (en) | 2018-04-09 | 2019-04-03 | Coating fluid and its functional membrane containing liquid crystal capsule |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110358339A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114578599A (en) * | 2022-03-24 | 2022-06-03 | 信利光电股份有限公司 | Display module assembly and attaching method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0258025A (en) * | 1988-08-24 | 1990-02-27 | Fuji Photo Film Co Ltd | Liquid crystal display element |
| KR20000028334A (en) * | 1998-10-28 | 2000-05-25 | 김충섭 | Polymer liquid crystal emulsion stabilized by acrylamide copolymer and liquid crystal composite film and preparation method thereof |
| KR20160052092A (en) * | 2014-11-04 | 2016-05-12 | 이미지랩(주) | Display device having the nano-sized lc layer |
| CN106575056A (en) * | 2014-09-02 | 2017-04-19 | 捷恩智株式会社 | Liquid crystal capsule and method for producing same |
| CN107108453A (en) * | 2015-01-14 | 2017-08-29 | 捷恩智株式会社 | Compound, liquid-crystal composition and liquid crystal display cells with polymerism base |
-
2019
- 2019-04-03 CN CN201910265497.2A patent/CN110358339A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0258025A (en) * | 1988-08-24 | 1990-02-27 | Fuji Photo Film Co Ltd | Liquid crystal display element |
| KR20000028334A (en) * | 1998-10-28 | 2000-05-25 | 김충섭 | Polymer liquid crystal emulsion stabilized by acrylamide copolymer and liquid crystal composite film and preparation method thereof |
| US6270691B2 (en) * | 1998-10-28 | 2001-08-07 | Korea Research Institute Of Chemical Technology | Polymer liquid crystal emulsion stabilized by water soluble copolymer, liquid crystal composite film and method for preparing thereof |
| CN106575056A (en) * | 2014-09-02 | 2017-04-19 | 捷恩智株式会社 | Liquid crystal capsule and method for producing same |
| KR20160052092A (en) * | 2014-11-04 | 2016-05-12 | 이미지랩(주) | Display device having the nano-sized lc layer |
| CN107108453A (en) * | 2015-01-14 | 2017-08-29 | 捷恩智株式会社 | Compound, liquid-crystal composition and liquid crystal display cells with polymerism base |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114578599A (en) * | 2022-03-24 | 2022-06-03 | 信利光电股份有限公司 | Display module assembly and attaching method thereof |
| CN114578599B (en) * | 2022-03-24 | 2023-09-22 | 信利光电股份有限公司 | Attaching method of display module and display module |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI409320B (en) | Liquid crystal composition and liquid crystal display device | |
| KR102084278B1 (en) | Liquid crystal composite and liquid crystal display element | |
| TWI509055B (en) | Liquid crystal composition and liquid crystal display device | |
| TWI609069B (en) | Liquid crystal display element, and liquid crystal composition and use thereof | |
| TWI509057B (en) | Liquid crystal composition and liquid crystal display element | |
| CN105339464B (en) | Liquid-crystal composition and application thereof and liquid crystal display cells | |
| TWI461512B (en) | Lcd element | |
| CN110878214B (en) | Liquid crystal composition, use thereof, and liquid crystal display element | |
| TW201516133A (en) | Liquid crystal composition and use thereof, and liquid crystal display element | |
| TWI550075B (en) | Liquid crystal composition and use thereof, and liquid crystal display device | |
| TWI535829B (en) | Liquid crystal composition and liquid crystal display element | |
| KR20150093166A (en) | Liquid crystal composition and liquid crystal display element | |
| TW201231630A (en) | Liquid crystal medium and liquid crystal display | |
| CN109844066A (en) | Liquid crystal complex and liquid crystal light modulation element | |
| TW201333174A (en) | Liquid crystal composition and use thereof, and liquid crystal display element | |
| TW201502251A (en) | Liquid crystal composition and liquid crystal display device | |
| TW201444958A (en) | Liquid crystal composition, use thereof, and liquid crystal display device | |
| TW201600587A (en) | Liquid-crystal display element, liquid crystal composition and liquid crystal alignment film | |
| TW201341512A (en) | Liquid crystal composition and usage thereof, and liquid crystal display element | |
| TWI599641B (en) | Liquid crystal composition and its use, and liquid crystal display element | |
| CN108139629A (en) | Liquid crystal display element | |
| CN110358339A (en) | Coating fluid and its functional membrane containing liquid crystal capsule | |
| CN104152155B (en) | A kind of low viscous high Negative dielectric anisotropic liquid crystal mixture of high birefringence rate and application thereof | |
| JP2019185024A (en) | Coating liquid containing liquid crystal capsules, and functional film produced therewith | |
| CN110872521B (en) | Liquid crystal composition, liquid crystal display element and use for liquid crystal display element |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20191022 |